Azodyestuff



Patented July 25, 1933 UNITED STATES PATEN- QFECE ALBERT SCHMELZER, FRITZ BALLAUF, AND FRIEDRICH MUTE, 0F ELIBERIEELD,GER- MANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A GOR- PORATION OF DELAWARE Azomznsrtrrr 7 No Drawing. Application filed November 14, 1929, Serial No. 407,275, and in Germany November 16,1928.

The present invention relates to water-insoluble azodyestulfs and more particularly to azodyestufit's of the probable general formula:

co-un-n wherein It stands for a radical of the benl6 zene or naphthalene series and R stands for the residue of a diazotizable aromatic or heterocyclic amine. 7

These new azodyestufis which are obtainable by coupling a diazotized aromatic or heterocyolic amine with a Q-hydroxy-carbazole-S-carboxylic acid arylamide either on the fibre, in substance oron a substratum, possess very good properties of fastness especially to light. The shades of these dyestufi's are of the most dillerent kind, for instance yellow, red-brown, blue and Violet shades are obtainable, according to the amine used in their preparation. I V

Inthe dry state the dyestuffs form yellow to dark powders which yield upon reduction :with hydrochloric acid and stannous chloride '1 mol of a 1-amino-2-hydroXy-carbazole-3- carboxylic acid arylamide and 1 mol of an aromatic or heterocyclic amine.

Our invention is illustrated by the following examples without being limited thereto:

Example 1.The well boiled and dried cotton yarn is impregnated by a solution of 3 gm. Q-hydrOXy-carbazole-3-carb-oxylic acid- 40 u-naphthalide, 6 cc. of an aqueous sodium hydroxide solution of 34 Be. and 6 cc. of Turkey red oil in one liter, wrung out,'rins'ed and soaped without drying and then developed in adiazo solution, neutralized with sodium acetate, containing 2 gr n. of EZ-amino- The 2ehydroxycarbazole-3-carboxylic acidarylamidesmentioned are obtainable from 2-hydroxycarbazole-8-carboXylic acid and an aromatic amine, according to the usual methods for instance, by condensation in a boiling toluenesolution by means ofphosphorus trichlorideor by acting upon the acid chlorides with amines.

-; Ewample 2.When-using 3 gm. of2 hydroXycarbazole-3-carboXylic acid o-toluidide' instead of the a-naphthyl-amide used in EX- ample 1 and 1-diazo-2-methoXy-5-nitrobenzene as coupling component and working in the samemanner as indicated in Example 1, a dyestufi of the probableformula:

will be obtained having excellent fastness propertiesand a red-brown shade.

The following table shows ther combinations and their a series of furshades:

The 2-hydroazycarbaeole-3-carbowylic aeid-awilide Combined with Yields shades Dianisidine Blue black o-phenetidine-azo-a-naphthylamine Bluish mnitro-o-anisidine Yellow-brown p-nitro-o-anisidine Brown 2-amino-carbazo1e Red-brown Q-ethyl-B-amino-carbazole Red-brown The QJLydrOaycaMae Ze-S-carbowylic aeid-a-naphthatide Combined with Yields shades Dianisidine 7 Dark blue o-phenetidine-azo-a-naphthylamine Deep-black m-nitro-o-anisidine Red-brown p-nitro-o-anisidine Reddish brown 2amin0-carbazo1e Brownish Bordeaux Bordeaux 9-ethy1-3-amino-carbazole The 2-hydrowycarbaeole-fi-carbowyllc acid-,B-naphthalide c 7 Combined with Yields shades 5-nitro-o-anisidine 7 Brown 2-ammo-carbazole Brownish Bordeaux 9-ethyl-3-amino-carbazo1e Bordeaux The z-hydromyca/rbazole-8-cafbowylic acid-p-anisidide Combined with Yields shades 2-an1ino-carbazo1e' Brownish' Bordeaux Q'ethy1-3-amino-carbazole Bordeaux 2, 5-diohlor-aniline Yellowish brown 5-nitro-2-anisidine Reddish brown The 2-hydro'zcycarbazvole- -carbowyl'ic-o'anisidide 5-nitro-2-anisidine 1 Brown We claim: I i 1. As new products water-insoluble azodyestuifs of the probable general formula:

u 1 v N CONH-R wherein R- stands for a radical of the benzene or naphthalene series and R stands for the V v residue of a diazotizable aromatic or hetero- 2. As a new product the azodyestuff of the probable formula:

and yielding when produced on the fiber red brown shades of excellent fastness properties, and yielding upon reduction with hydrochloric acid and stannous chloride 1 mol.

of 1-amino-2-hydroxycarbazole 3 carboxylic acid o-toluidide and 1 mol of 1-amino-2- meth0Xy-5-nit1'obenzene.

3. Fiber dyed with the dyestuif as claimed inclaim 1.

4. Fiber dyed with the dyestuif as claimed j in claim 2.

5. As a new product the azo dyestui'f of the probable formula:

h? H N I I oH ooNH yielding fast brownish'Bordeaux-red shades when produced on the fiber, and yielding upon reduction with hydrochloric acid and stannous chloride 1 mol of l-amino-2-hy- 11o droxycarbazole-3 -carboxylic acid a-nap'hthylamide and 1 mol of 2-aminocarbazole.

6. Fiber dyed with the dyestuff as claimed in claim 5.7 V 7. As new products water-insoluble azodyestuffs of the probable general formula:

V v R1 wherein R and R stand for radicals of the benzene -or naphthalene series, being very valuable azodyestufls of yellow to black shades and yielding upon reduction with hydrochloric acid and stannous chloride 1 mol of a 1-amino-2-hydroxycarbazole-3-carboxylic acid arylamide and 1 mol of an aromatic amine of the series. a v

8. As new products water-msoluble azobenzene or naphthalene dyestufi's of the probable general formula:

R1 I 111 I] N wherein R and R stand for radicals of the benzene or naphthalene series which may be a substituted by alkyl, nitro, alkoxy, a radical of the benzene azo series or halogen, being very valuable azodyestuffs of yellow to black shades and yielding upon reduction with hydrochloric acid and stannous chloride 1 mol of a l-amino-2-hydroxy-carbazole-3-car boxylic acid arylamide and 1 mol of anaro-v matic amine of the benzene or naphthalene series.

9. As new products water-insoluble azo-' dyestufis of the probable general formula:

' series.

wherein R and R stand forradicals of the benzene or naphthaleneseries which'may be substituted by methyl, nitro, methoxy, a radi- V cal of the benzene-azo series or chlorine, being very valuble azodyestufi's of yellow to black shades and yielding upon reduction with hydrochloric acid and stannous chloride 1 mol of a 1-amino-2-hydroxycarbazole-3- wherein'R and R stand for benzene nuclei which may be substituted by chlorine, methyl, methoxy or nitro, being very Valuable azodyestuffs of yellow to black shades and yielding upon reduction with'hydrochloric acid and stannous chloride 1 mol of a l-amino- 2-hydroXy-carbazole-3-carboxylic 7 acid arylamide and 1 mol of an amine of the'benzene ALBERT SCHMELZER. FRITZ BALLAUF. FRIEDRICH 'MUTH. V 

